The present invention relates to a resin composition and a method for producing the same, and in particular to a curable resin composition useful as a raw material for urushi(oriental lacquer)-like coating, a material for forming a coating film, a compound for recording material, a raw material for ink, a raw material for coating, a raw material for adhesive, a raw material for an epoxy resin, a raw material for photoresist, a raw material for antioxidant, a molding material, a raw material for laminated material, a raw material for adhesive, a raw material for binder, a raw material of a phenol resin for casting, a raw material of a phenol resin for rubber blending, and a raw material of a phenol resin for fiber plate; and a method for producing the same.
A wide variety of a phenol-compound-containing vegetable oil are known, among which urushiol, thitsiol, laccol, and cardanol, which are all obtained from sap of an Anacardiaceae plant, have been used as coatings (raw material for resin for dyes). Urushiol, thitsiol, or laccol forms a cured coating film at room temperature by an enzymatic catalyst (laccase) contained in the sap. The enzymatic catalyst is labile to heat, generally, when these resins are heated at 70xc2x0 C. or more, the enzyme is inactivated, to reduce the catalytic activity, thus preventing the formation of a cured film, but the resins can be cured at about 130xc2x0 C. or more. The cured coating film is not only excellent in hardness, with excellent in flexibility, but also in beauty, such as gloss, so it has been used for producing urushi ware since ancient times. Further, a urushi coating called kuro-urushi is made up of about 95% or more solids, the remaining being water, and thus the urushi coating can be regarded not only as a solvent-free type coating or a high-solid coating of a room temperature-curing type, but also as an organic coating film having high durability, as can be seen in lacquered remains artifacts as old as 1000 years or more. Further, the urushi coating can also be regarded as a coating with little affection on the natural environment, because, unlike synthetic resin coatings, the urushi coating neither uses a large amount of organic solvent nor requires high temperatures for curing. As described above, the urushi coating is an ideal coating at present, when the consciousness of global environmental problems is increasing. However, there are the problems that the urushi is produced only a small amount; it is expensive, and it is poison for the skin, etc.
On the other hand, a cashew nut shell liquid, obtained from the Anacardiaceae cashew tree (Anacardium occidentale), is produced in a large amount; it is inexpensive; it occurs as a by-product in preparation of edible kernel, and it is industrially useful as a urushi-like coating and a friction material (brake linings, brake pads), etc.
The cashew nut shell liquid contains a phenol compound such as anacardic acid which is a major component. The number of carbon atoms in the side chain of this compound is 15, and the number of an unsaturated bond in the side chain is 0 to 3 (average=about 2). Additionally, it is known that cardanol, cardol, 2-methyl cardol, and the like, are contained in the cashew nut shell liquid. The cashew nut shell liquid may be used as such for industrial purposes, but a material whose major component is cardanol, which is obtained by heat-treating the cashew nut shell liquid, to decarbonate a carboxyl group in anacardic acid, is generally used as a raw material for industry.
This cashew nut shell liquid (including the heat-treated material) is generally converted into cashew varnish for use in the various utilities described above, and, as can be seen from the extreme similarity in structure between cardanol and urushiol mentioned above, the cashew nut shell liquid has been used as a substitute for urushi. In the case of the cashew nut shell liquid unlike urushi, however, the curing reaction does not proceed by the enzymatic catalyst contained in the sap, and therefore, hexamethylenetetramine, which is a condensate of formaldehyde, and ammonia, or of formalin is reacted with the raw oil whose major component is cardanol, to produce cashew varnish (cardanol prepolymer). Then, a metal drier usually used in an oily coating is added thereto, as a catalyst, to oxidize the site of side-chain olefins, and other materials, such as predetermined pigments, etc., are mixed therewith, to give a general cashew resin coating as an oxidative-polymerizable coating. The cashew resin coating produced in this manner may cause the generation of formalin (formaldehyde), which is highly toxic to the human body, not only during the production process but also after a product is formed therefrom. However, the consciousness toward environmental problems has increased in recent years, and from the viewpoint of deodorization of the living environment and safety, health, etc., for the human body, there is a demand for a synthesis process that does not use highly toxic formalin (formaldehyde) in the cashew coating, as well as for development of a resin that does not generate formalin (formaldehyde).
Further, the phenol compound in the vegetable oil, such as the cashew nut shell liquid, generally have an unsaturated aliphatic group, such as an alkenyl group in the side chain, and in consideration of using the aforementioned phenol compound as an oxidative-polymerizable resin for a coating, which resin is curable at a room temperature, it is important that the reaction be suitably regulated so that the side chain in the phenol compound do not react during the polymerization reaction. However, when the polymerization reaction was carried out using a conventional catalyst without using formalin, hexamethylenetetramine, etc., it is difficult to regulate the reaction as only the site of the aromatic ring having a phenolic hydroxyl group undergoes oxidative polymerization. For example, JP-A-58-47079 describes a method for producing cashew dust by adding an acid to a cashew nut shell liquid, and then heat-polymerizing it, and then curing and grinding it, and in this process, a polymer called cashew dust, which is insoluble in solvent, is obtained, and it is not usable as a coating resin. Even if the product is not the dust but a polymer which is soluble in an organic solvent, the polymerization reaction proceeds in an alkenyl group in the side chain in the cashew nut shell liquid (shown in Comparative Example 2 below), and thus the reactivity of the remaining phenol site, which do not react yet, is utilized to prepare a cured product therefrom, but aldehydes, such as formalin, etc., are used often for linking the phenol site, so it is problematic that the toxicity of aldehyde cannot be solved.
On the other hand, it have already been known that phenols can be polymerized using an iron complex as the catalyst in the presence of oxygen (e.g., JP-A-49-26264). Further, it have already been known that phenols can be polymerized using a transition metal complex as the catalyst in the presence of peroxides (e.g., JP-A-8-53545 and Polymer Bulletin, 42, 125 (1999)). In these processes, however, the reaction materials are phenol compounds themselves, and these prior art documents do not show any example in which a phenol-compound-containing vegetable oil are used as a monomer component. Further, these prior art examples do not describe about a production of a curable resin composition derived from a vegetable oil by oxidative polymerization of only phenolic hydroxyl group, in a vegetable oil of nature origin containing multiple phenol compounds having an unsaturated aliphatic group such as an alkenyl group in the side chain.
Further, in Japanese Patent No. 3030363, the present inventors revealed a liquid resin formed by polymerizing a cashew nut shell liquid by use of an enzymatic catalyst, but the catalyst for obtaining the resin was not a transition metal complex.
The present invention relates to a resin composition and a method for producing the same, and it provides a curable resin composition useful as a raw material for urushi-like coatings, a friction material, a brake lining material, a brake pad material, a material for formation of coating films, a compound for recording materials, a raw material for ink, a raw material for coatings, a raw material for adhesives, a raw material for epoxy resin, a raw material for photoresist or antioxidants, and a starting material for functional polymers, and a method for producing the same.
The above-mentioned and other objects, features and advantages of the present invention will become more apparent from the following descriptions.
The present invention relates to a curable resin composition comprising a resin formed in the presence of a transition metal complex by polymerizing an oxidative-polymerizable compound that contains a phenol-compound-containing vegetable oil.
Hereinafter, the present invention is described in more detail.
A wide variety of a phenol-compound-containing vegetable oil used in the present invention are known (those described in e.g. Chem. Soc. Rev., 8, 499 (1979)), and those vegetable oils derived from each of the genera Anacardicae, Gymnospermae, Compositae, Lichens, and Proteacae can be used. Examples of phenol compounds in the phenol compound-containing vegetables oils include anacardic acid, anagiganoic acid, pelandjauic acid, ginkgoic acid, ginkgophosphoric acid, cardanol, cardol, methyl cardol, urushiol, thitsiol, rhengol, laccol etc. The total content of a variety of these phenol compounds in the vegetable oils used in the present invention is generally 50% by weight or more, preferably 70% by weight or more. Specifically, such vegetable oils include a cashew nut shell liquid obtained from a cashew tree (Anacardium occidentale).
This cashew nut shell liquid contains the whole of viscous liquids extracted from cashew nuts is born by the cashew tree. The components in the cashew nut shell liquid are not particularly limited, and include compounds such as anacardic acid, cardanol, cardol and methyl cardol, and preferable include a cashew nut shell liquid whose major component is cardanol obtained by high-temperature treatment of cashew oil whose major component is anacardic acid. These components are monovalent phenol alkyl or alkenyl derivatives, and the alkenyl group in the side chain consists of monoene, diene and triene, and may also be used as a mixture thereof in the present invention. In the present invention, a viscous liquid extracted from cashew nuts may be used as it is or after purification or treatment such as modification. In the case of the cashew Tn, nut shell liquid containing anacardic acid, it is possible that the hydroxyl group and carboxyl group in anacardic acid forms a chelate with a transition metal in the transition metal complex used in the present invention, and thus the cashew nut shell liquid whose major component is cardanol can be preferably used.
The phrase xe2x80x9cmajor component is cardanolxe2x80x9d means that cardanol presents at an amount of generally 80% by weight or more in the cashew nut shell liquid.
Further, a phenol-compound-containing vegetable oil of nature origin, such as a cashew nut shell liquid, are used preferably as the phenol-compound-containing vegetable oil in the producing process of the present invention, but besides the vegetable oils described above, various oxidative-polymerizable compounds, such as phenols, naphthols, and aromatic amines, can be contained to carry out the copolymerization reaction. The phenols, naphthols and aromatic amines, and the amounts of use thereof can be selected in various physical properties demanded according to the use and object of the resulting vegetable oil polymers containing phenol compounds, and these materials can be used singly or in combination thereof. Although the ratio of compounds used as such copolymerization reaction components is arbitrary, the amount of the phenols and naphthols is generally 5000 mol % or less, preferably 500 mol % or less, most preferably 100 mol % or less, relative to the phenol-compound-containing vegetable oil (relative to the total of phenol compounds contained therein), further, the amount of the aromatic amines is generally 5000 mol % or less, preferably 500 mol % or less, and most preferably 100 mol % or less.
Such phenols include, for example, alkyl phenols such as o-cresol, m-cresol, p-cresol, p-octyl phenol, p-dodecyl phenol, 2,3-dimethyl phenol, 2,4-dimethyl phenol, 2,5-dimethyl phenol, 2,6-dimethyl phenol, 3,4-dimethyl phenol, 3,5-dimethyl phenol, o-ethyl phenol, m-ethyl phenol, 2,4,6-dimethyl phenol, p-t-butyl phenol, 2,4-di-t-butyl phenol, 2,6-di-t-butyl phenol and p-t-amyl phenol, polyvalent phenols such as hydroquinone, catechol, resorcinol, pyrogallol, urushiol, thitsiol and laccol, halogenated phenols such as o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,4,6-trichlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-fluorophenol, m-fluorophenol and p-fluorophenol, amino phenols such as o-amino phenol, m-amino phenol and p-amino phenol, bisphenol A, p-(xcex1-cumyl) phenol, p-phenyl phenol, guaiacol, guethol, and phenol.
Specific examples of the naphthols include xcex1-naphthol, xcex2-naphthol, 1,4-dihydroxynaphthalene, etc.
Specific examples of the aromatic amines include aniline, o-anisidine, p-anisidine, 2,4-xylidine, 3,4-xylidine, p-cresidine, 4,4xe2x80x2-diamino-3,3xe2x80x2-diethyl diphenyl methane, 4,4xe2x80x2-diaminobenzanilide, diaminodiphenyl ether, 3,3xe2x80x2-dimethyl-4,4xe2x80x2-diaminodiphenyl methane, sulfanilic acid, etc.
In the method for producing a curable resin composition comprising a resin formed, in the presence of a transition metal complex catalyst, by polymerizing an oxidative-polymerizable compound that contains a phenol-compound-containing vegetable oil of the present invention, it is considered that the polymerization mechanism is the radical coupling reaction of phenoxy radicals formed by oxidation reaction (dehydrogenation reaction) of phenol compounds in the vegetable oils, by the transition metal complex. This phenoxy radical has a resonance structure (carbon radical and oxygen radical), and it is considered that these phenoxy resonance radicals are very unstable and immediately subjected to coupling reaction of two molecules (dimerization reaction). The polymerization of dimers or more is considered to proceed as follows: The dimers, formed by the coupling reaction described above, further undergo oxidation reaction (dehydrogenation reaction) by the transition metal complex to form phenoxy radicals which in turn are subjected to coupling with phenoxy radicals of monomers or with phenoxy radicals of dimers or more oligomers.
Further, it is considered that the formation of phenoxy radicals can occur due to radical substitution reaction between phenoxy radicals of monomers, and monomers or oligomers, and phenoxy radicals are also formed in this case in the same manner as described above, and thus the polymerization reaction is considered to proceed in the same manner as described the above. Accordingly, the resin of a phenol-compound-containing vegetable oil, which is obtained in the present invention, comprises the polymers having units bound via oxyphenylene to phenylene bonds at random in the site of the aromatic rings of a phenol-compound-containing vegetable oil, wherein aliphatic unsaturated double bonds in their side chain remain. The degree of the remaining aliphatic unsaturated double bond in the side chain vary according to various polymerization conditions such as the type and amount of the transition metal complex, which is used, the reaction temperature and the solvent, but is generally 70% or more, preferably 80 to 100%, more preferably 100%.
By selecting various conditions for the polymerization reaction in the present invention, it is possible to regulate whether the double bonds in the side chain are allowed to remain, or whether a part or most of the double bonds are crosslinked. Specifically, whether the curable resin composition can be obtained or not is determined depending on the type of the reaction solvent and the amount of the transition metal complex relative to the phenol compounds in vegetable oils. The iodine value of the resin composition of the present invention is generally 50 to 500, preferably 100 to 500.
The transition metal complex, which is used in the present invention, can be used singly or as a mixture thereof. Its amount may be used in an arbitrary amount, and suitably regulated depending on the catalytic activity of the transition metal complex which is used in the present invention, but it can be used generally in the order of 0.0001 to 30 mol %, preferably 0.01 to 10 mol % or thereabout, relative to the phenol-compound-containing vegetable oil. Further, as the catalyst, the transition metal compound can be mixed with its corresponding ligand during the reaction. In this case, the ligand may be used in an arbitrary amount, however, generally preferably in an about 0.1 to 10 molar equivalence relative to the transition metal.
The transition metal atom in the transition metal complex of the present invention is a transition metal atom in the groups 3A to 7A, 8, 1B and 2B in the elemental periodic table (IUPAC nomenclature in inorganic chemistry, Revised Ed., 1989). It is preferably a transition metal atom in the first transition element series, more preferably iron, cobalt, vanadium, chromium, manganese, nickel, copper, or vanadium oxide. It is more preferably iron, cobalt, copper or manganese.
The ligand in the transition metal complex of the present invention is a ligand whose ligand atom is a nitrogen atom, phosphorus atom, oxygen atoms, or sulfur atom, respectively.
The ligand in the present invention refers to a molecule or an ion which is bound via a coordinate bond to a certain atom, as described in xe2x80x9cKagaku Daijiten (Large Dictionary of Chemistry)xe2x80x9d (First Ed., Tokyo Kagaku Dojin, 1989). The atom participating directly in the coordinate bond is called a ligand atom. Monodentate ligand, bidentate ligand, tridentate ligand, quadridentate ligand, and quinquedentate ligand are ligands wherein each number of ligand atoms is 1, 2, 3, 4 and 5, respectively.
In the transition metal complex of the present invention, the number of transition metal atoms per said ligand may be one or more, preferably one or more and not more than the number of ligand atoms in the ligand, and more preferably one.
The ligand in the transition metal complex of the present invention is not particularly limited insofar as the ligand has an ability to polymerize the phenol-compound-containing vegetable oil component, and the bidentate ligand, quadridentate ligand, and quinquedentate ligand can be preferably used.
Specific examples of the bidentate ligand include anions obtained by removing one or more protons from ethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,2-butane diol, 2,3-butane diol, 2,3-dimethyl-2,3-butane diol, 1,2-cyclohexane diol, 1,2-ethane dithiol, 1,3-propane dithiol, catechol, hydroxyacetic acid, 2-hydroxypropionic acid, 2-hydroxybutyric acid, ethyl hydroxyacetate, hydroxyacetone, 2-ketopropionic acid, 2-ketobutyric acid, ethyl 2-ketopropionate, acetyl acetone, salicylaldehyde, salicylic acid, ethyl acetoacetate, malonic acid, diethyl malonate, glycine, alanine, valine, leucine, phenyl alanine, monoethanol amine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 3-amino-2-butanol, 3-amino-2,3-dimethyl-2-butanol, 2-amino-1-cyclohexanol, N-methyl ethanol amine, N-ethyl ethanol amine, N-propyl ethanol amine, N-butyl ethanol amine, N-phenyl ethanol amine, N-methyl propanol amine, N-phenyl propanol amine, N,N-dimethyl ethanol amine, N,N-diethyl ethanol amine, N-salicylidene methyl amine, N-salicylidene ethyl amine, N-salicylidene propyl amine, N-salicylidene butyl amine, N-salicylidene aniline, 4-(N-methylimino)-2-pentanone, 4-(N-ethylimino)-2-pentanone, 4-(N-propylimino)-2-pentanone, 4-(N-phenylimino)-2-pentanone, 2-(N-methylimino) propionic acid, 3-(N-methylimino)propionic acid, ethyl 3-(N-methylimino)propionate, 2-(N-methylimino) butyric acid, 2-(N-methylimino)propanol, etc.; and neutral molecules such as 2,3-butane dione, 3,4-hexane dione, 2,5-dimethyl-3,4-hexane dione, 2,2-dimethyl-3,4-hexane dione, 2,2,5,5-tetramethyl-3,4-hexane dione, 1,2-cyclohexane dione, 2-(N-methylimino)-3-butanone, 2-(N-ethylimino)-3-butanone, 2-(N-propylimino)-3-butanone, 2-(N-butylimino)-3-butanone, 2-(N-phenylimino)-3-butanone, 3-(N-methylimino)-3-hexanone, 2-(N-methylimino)-cyclohexanone, methyl 2-(N-methylimino)-propionate, ethyl 2-(N-methylimino)-butyrate, etc.
Specific examples of the quadridentate ligand include tris(2-pyridyl methyl) amine, tris(2-imidazolyl methyl)amine, tris(1-methyl-2-imidazolyl methyl)amine, tris(2-benzimidazolyl methyl)amine, tris(2-benzoxazolyl methyl)amine, tris(2-benzthiazolyl methyl)amine, tris(1-pyrazolyl methyl)amine, tris(3,5-dimethyl-1-pyrazolyl methyl)amine, tris(3,5-dipropyl-1-pyrazolyl methyl)amine, tris(3,5-diphenyl-1-pyrazolyl methyl)amine, nitrilotriacetic acid, nitrilotriethanol, nitrilotri-1-propanol, tris(2-pyridyl-2-ethyl)amine, tris(1-pyrazolyl-2-ethyl)amine, N-(2-mercaptoethyl)-N,N-diethanol amine, N-(diphenyl phosphinoethyl)-N,N-diethanol amine, triethylene glycol, tripropylene glycol, triethylene tetramine, N,Nxe2x80x2xe2x80x3-dimethyl triethylene tetramine, -N,N,Nxe2x80x2xe2x80x3,Nxe2x80x2xe2x80x3-tetramethyl triethylene tetramine, N,Nxe2x80x2-bis(2-hydroxyethyl)ethylene diamine, N,Nxe2x80x2-bis(3-hydroxypropyl)ethylene diamine, N,Nxe2x80x2-ethylene diamine diacetic acid, N,Nxe2x80x2-bis(2-pyridyl methyl)ethylene diamine, N,Nxe2x80x2-bis(2-imidazolyl methyl)ethylene diamine, N,Nxe2x80x2-bis(2-benzimidazolyl methyl)ethylene diamine, N,Nxe2x80x2-bis(2-mercaptoethyl)ethylene diamine, N,Nxe2x80x2-bis(diphenyl phosphinoethyl)ethylene diamine, N,Nxe2x80x2-disalicylidene ethylene diamine, N,Nxe2x80x2-bis(1-methyl-3-oxobutylidene) ethylene diamine, N-2-hydroxyethyl-Nxe2x80x2-salicylidene ethylene diamine, N-2-hydroxyethyl-Nxe2x80x2-salicylidene-1,3-propylene diamine, N-3-hydroxypropyl-Nxe2x80x2-salicylidene-1,3-propylene diamine, N-3-hydroxypropyl-Nxe2x80x2-salicylidene ethylene diamine, N-2-dimethyl aminoethyl-Nxe2x80x2-salicylidene ethylene diamine, N-2-pyridyl methyl-Nxe2x80x2-salicylidene ethylene diamine, N,Nxe2x80x2-bis(2-amino-3-benzylidene)ethylene diamine, 1-(diacetylmonoxime imino)-3-(diacetyl monoxymatoimino)propane, 12-crown-4,1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetraazacyclotetradecane-5,7-dione, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, 1,4,7,10-tetrathiacyclododecane, 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene, 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraene, porphyrin, phthalocyanine, etc., or anions obtained by removing one or more protons from the aforementioned compounds.
Further, specific examples of the quinquedentate ligand include tetraethylene glycol, tetrapropylene glycol, tetraethylene pentamine, N,Nxe2x80x2xe2x80x3-dimethyl tetraethylene pentamine, N,N,Nxe2x80x2xe2x80x3,Nxe2x80x2xe2x80x3-tetramethyl tetraethylene pentamine, N,Nxe2x80x3-bis(2-hydroxyethyl)diethylene triamine, N,Nxe2x80x3-bis(3-hydroxypropyl)diethylene triamine, N,Nxe2x80x3-diethylene triamine, diacetic acid, N,Nxe2x80x3-bis(2-pyridyl methyl)diethylene triamine, N,Nxe2x80x3-bis(2-imidazolyl methyl)diethylene triamine, N,Nxe2x80x3-bis(2-benzimidazolyl methyl)diethylene triamine, N,Nxe2x80x3-bis(2-mercaptoethyl) diethylene triamine, N,Nxe2x80x3-bis(diphenyl phosphinoethyl) diethylene triamine, N,Nxe2x80x3-disalicylidene diethylene triamine, N,Nxe2x80x3-bis(1-methyl-3-oxobutylidene)diethylene triamine, N-2-hydroxyethyl-Nxe2x80x3-salicylidene diethylene triamine, N-3-hydroxypropyl-Nxe2x80x3-salicylidene diethylene triamine, N-3-hydroxypropyl-Nxe2x80x2-salicylidene ethylene diamine, N-2-dimethyl aminoethyl-Nxe2x80x3-salicylidene diethylene triamine, N-2-pyridyl methyl-Nxe2x80x3-salicylidene diethylene triamine, N,Nxe2x80x3-bis(2-amino-3-benzylidene) diethylene triamine, 1,5-bis(salicylidene amino)-3-pentanol, 2,6-bis[N-(2-hydroxyethyl)iminoethyl]-4-methyl phenol, 2,6-bis[N-(3-hydroxypropyl)iminomethyl]-4-methyl phenol, 2,6-bis[N-(2-hydroxyphenyl)iminomethyl]-4-methyl phenol, 2,6-bis[N-(2-pyridyl methyl)iminomethyl]-4-methyl phenol, 2,6-bis[N-(2-pyridyl ethyl)iminomethyl]-4-methyl phenol, 2,6-bis[N-(2-dimethylaminoethyl)iminomethyl]-4-methyl phenol, 2,6-bis[N-(2-pyridyl methyl) aminomethyl]-4-methyl phenol, 2,6-bis[N-(2-pyridyl ethyl)aminomethyl]phenol, 15-crown-5,1,4,7,10,13-pentathiacyclopentadecane, etc., or anions obtained by removing one or more protons from the aforementioned compounds.
The ligand atom in the ligand in the transition metal complex of the present invention is preferably a nitrogen atom and/or an oxygen atom.
The transition metal complex of the present invention is preferably a transition metal complex represented by the following formula (I), (II), (III), or (IV): 
wherein M represents a residue containing a transition metal atom; R1 and R3 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, Oxe2x88x92, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, an amino group, or a substituted amino group; R2 represents a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a hydrocarbon oxycarbonyl group, a substituted hydrocarbon oxycarbonyl group, a cyano group, a nitro group, or a halogen atom; R1 and R2, and/or R2 and R3 may form a ring; and n is an integer of 1 to 
wherein M represents a residue containing a transition metal atom; R4 and R9 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, Oxe2x88x92, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, an amino group, or a substituted amino group; R5 and R8 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a hydrocarbon oxycarbonyl group, a substituted hydrocarbon oxycarbonyl group, a cyano group, a nitro group, or a halogen atom; R6 and R7 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, or Oxe2x88x92; R10 represent a divalent hydrocarbon group or substituted hydrocarbon group, and R4 and R5, and/or R8 and R9 may form a ring; 
wherein M represents a residue containing a transition metal atom; R4 and R9 each independently represent a, hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, Oxe2x88x92, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, an amino group, or a substituted amino group; R5 and R8 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a hydrocarbon oxycarbonyl group, a substituted hydrocarbon oxycarbonyl group, a cyano group, a nitro group, or a halogen atom; R6 and R7 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, or Oxe2x88x92; R11 and R12 each represent a divalent hydrocarbon group or substituted hydrocarbon group; R13 represents a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group; and R4 and R5, and/or R8 and R9 may form a ring, 
wherein M represents a residue containing a transition metal atom; R14 to R29 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, Oxe2x88x92, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, an amino group, or a substituted amino group, a hydrocarbon oxycarbonyl group, a substituted hydrocarbon oxycarbonyl group, a cyano group, a nitro group, or a halogen atom, or Oxe2x88x92; R14 and R15, and/or R15 and R16, and/or R16 and R17, and/or R18 and R19, and/or R19 and R20, and/or R20 and R21, and/or R22 and R23, and/or R24 and R25, and/or R26 and R27, and/or R27 and R28, and/or R28 and R29 may form a ring.
The substituted hydrocarbon oxy group in the aforementioned formula (I), (II), (III), or (IV) is a hydrocarbon oxy group substituted with a halogen atom, alkoxy group, amino group, etc., and specific examples thereof include a trifluoromethoxy group, 2-t-butyloxyethoxy group, 3-diphenyl aminopropoxy group, etc.
The substituted amino group in the aforementioned formula (I), (II), (III), or (IV) is preferably a substituted amino group having 1 to 20 total carbon atoms, and specific examples thereof include a methyl amino group, ethyl amino group, propyl amino group, butyl amino group, phenyl amino group, dimethyl amino group, diethyl amino group, dipropyl amino group, dibutyl amino group, methyl ethyl amino group, methyl propyl amino group, methyl butyl amino group, diphenyl amino group, dinaphthyl amino group, etc.
The hydrocarbon oxycarbonyl group in the aforementioned formula (I), (II), (III), or (IV) is preferably a hydrocarbon oxycarbonyl group having 1 to 20 total carbon atoms, and specific examples thereof include a methoxycarbonyl-group, ethoxycarbonyl group, propoxycarbonyl group, t-butyloxycarbonyl group, phenoxycarbonyl group, etc.
The substituted hydrocarbon oxycarbonyl group in the aforementioned formula (I), (II), (III), or (IV) is a hydrocarbon oxycarbonyl group substituted with a halogen atom, alkoxy group, amino group, etc., and specific examples thereof include a trifluoromethoxy carbonyl group, 2-t-butyloxyethoxy carbonyl group, 3-diphenyl aminopropoxy carbonyl group, etc.
The halogen atom in the aforementioned formula (I), (II), (III), or (IV) is preferably a chlorine atom, bromine atom, or iodine atom, more preferably chlorine atom or bromine atom.
In the aforementioned formula (II) or (III), R10, R11, and R12 are divalent hydrocarbon groups or substituted hydrocarbon groups, and specific examples thereof include alkylene groups such as methylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, etc., cycloalkylene groups such as 1,2-cyclopentylene group, 1,2-cyclohexylene group, etc., and arylene groups such as phenylene group, naphthylene group, etc., and preferable examples include a methylene group, ethylene group, 1,3-propylene group and 1,2-cyclohexylene group.
Specific examples of the bidentate ligand in the transition metal complex represented by the aforementioned formula (I) include acetyl acetone, 2,2,6,6-tetramethyl-3,5-heptane dione, trifluoroacetyl acetone, dibenzoyl methane, etc., or anions and the like obtained by removing one or more protons therefrom. Preferably, acetyl acetone can be used.
Specific examples of the quadridentate ligand in the transition metal complex represented by the aforementioned 3formula (II) include N,Nxe2x80x2-disalicylidene ethylene diamine, N-(3-oxopentylidene)-Nxe2x80x2-salicylidene ethylene diamine, N,Nxe2x80x2-bis(3-oxobutylidene)ethylene diamine, N,Nxe2x80x2-bis(3-aoxobutylidene)-1,3-propane diamine, N,Nxe2x80x2-bis(3-oxobutylidene)-1,2-phenylene diamine, N,Nxe2x80x2-bis(1-methyl-3-oxobutylidene)ethylene diamine, N,Nxe2x80x2-bis(3-oxopentylidene)ethylene diamine, N,Nxe2x80x2-bis(3-oxohexylidene)ethylene diamine, N,Nxe2x80x2-bis(4-methyl-3-oxopentylidene)ethylene diamine, N,Nxe2x80x2-bis(4,4-dimethyl-3-oxopentylidene)ethylene diamine, N,Nxe2x80x2-bis(4-phenyl-3-oxobutylidene)ethylene diamine, N,Nxe2x80x2-bis(4-trifluoromethyl-3-oxobutylidene)ethylene diamine, N,Nxe2x80x2-bis(2-cyano-3-oxobutylidene)ethylene diamine, N,Nxe2x80x2-bis(2-cyano-3-oxobutylidene)ethylene diamine, N,Nxe2x80x2-bis(2-nitro-3-oxobutylidene)ethylene diamine, N,Nxe2x80x2-bis(2-carboxylethylidene)ethylene diamine, N,Nxe2x80x2-bis[2-(methoxycarbonyl)ethylidene]ethylene diamine, N,Nxe2x80x2-5 bis[2-(dimethylaminocarbonyl)ethylidene]ethylene diamine, N,Nxe2x80x2-(1,2-ethylene)-bis(salicylic acid amide), N,Nxe2x80x2-(1,2-ethylene)-bis(malonic acid monomethyl monoamide), etc., or anions, etc., obtained by removing one or more protons therefrom.
Specific examples of the quinquedentate ligand in the transition metal complex represented by the aforementioned formula (III) include N,Nxe2x80x3-disalicylidene diethylene triamine, N-(3-oxopentylidene)-Nxe2x80x3-salicylidene diethylene triamine, N,Nxe2x80x3-bis(3-oxobutylidene)diethylene triamine, N,Nxe2x80x3-bis(3-oxobutylidene)-dipropylene triamine, N,Nxe2x80x3-bis(3-oxobutylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(1-methyl-3-oxobutylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(3-oxopentylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(3-oxohexylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(4-methyl-3-oxopentylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(4,4-dimethyl-3-oxopentylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(4-phenyl-3-oxobutylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(4-trifluoromethyl-3-oxobutylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(2-cyano-3-oxobutylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(2-cyano 3-oxobutylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(2-nitro-3-oxobutylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis(2-carboxylethylidene)-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x3-bis[2-(methoxycarbonyl)ethylidene]-Nxe2x80x3-methyl dipropylene triamine, N,Nxe2x80x3-bis[2-(dimethylaminocarbonyl) ethylidene]-Nxe2x80x2-methyl dipropylene triamine, N,Nxe2x80x2-(3-aza-1,5-pentylenelene)-bis(salicylic acid amide), N,Nxe2x80x2-(3-aza-1,5-pentylenelene)-bis(malonic acid monomethyl monoamide), etc., or anions, etc., obtained by removing one or more protons therefrom.
Further, the transition metal complex represented by the aforementioned formula (II) or (III) is more preferably the transition metal complex represented by the following formula (V) or (VI): 
wherein M represents a residue containing a transition metal atom; R6 and R7 each independently represent a hydrogen atom, a hydrocarbon group, or a substituted hydrocarbon group; R10 represents a divalent hydrocarbon group or substituted hydrocarbon group; R30 to R37 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a substituted amino group, a nitro group, or a halogen atom, 
wherein M represents a residue containing a transition metal atom; R6, R7, or R13 each independently represent a hydrogen atom, a hydrocarbon group, or a substituted hydrocarbon group; R11and R12 each independently represent a divalent hydrocarbon group or a substituted hydrocarbon group; R30 to R37 each independently represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, a substituted hydrocarbon oxy group, a substituted amino group, a nitro group, or a halogen atom.
M, the hydrocarbon group, the substituted hydrocarbon group, the divalent hydrocarbon group, or the substituted hydrocarbon group, the hydrocarbon oxy group, the substituted hydrocarbon oxy group, the substituted amino group, or the halogen atom, in the aforementioned formula (V) or (VI), include those exemplified in the aforementioned formula (II) or (III).
As R6; R7, R10, and R30 to R37 in the aforementioned formula (V), it is more preferable that R6 and R7 are each independently a hydrogen atom or a hydrocarbon group, R10 is an alkylene group, cycloalkylene group, or arylene group, and R30 to R37 are each independently a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a substituted amino group, a nitro group, a chlorine atom, or a bromine atom. Particularly preferably, R6 and R7 are each independently a hydrogen atom, a methyl group, or phenyl group, R10 is a 1,2-ethylene group, 1,3-propylene group, 1,2-cyclohexylene group, or 1,2-phenylene group, and R30 to R37 are each independently a hydrogen atom, a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, benzyl group, trifluoromethyl group, methoxy group, dimethylamino group, nitro group, chlorine atom, or bromine atom.
As R6, R7, R11 to R13, and R30 to R37 in the aforementioned formula (VI), it is more preferable that R6, R7, and R13 are each independently a hydrogen atom or a hydrocarbon group, R11 and R12 are each independently an alkylene group or an arylene group, and R30 to R37 are each independently a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a substituted amino group, a nitro group, a chlorine atom, or a bromine atom. Particularly preferably, R6, R7, and R13 are each independently a hydrogen atom, a methyl group, or a phenyl group, R11 and R12 are each independently a 1,2-ethylene group, 1,3-propylene group, or 1,2-phenylene group, and R30 to R37 are each independently a hydrogen atom, a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, benzyl group, trifluoromethyl group, methoxy group, dimethylamino group, nitro group, chlorine atom, or bromine atom.
Specific examples of the quadridentate ligand in the transition metal complex represented by the aforementioned formula (IV) includes, phthalocyanine, 1,4,8,11,15,18,22,25-octacarboxy-29H, 31H-phthalocyanine, 1,8,15,22-tetraphenoxy-29H, 31H-phthalocyanine, 2,9,16,23-tetra-t-butyl-29H, 31H-phthalocyanine, tetrakis(4-cumyl phenoxy)phthalocyanine, 1,8,15,22-tetrakis(phenyl thio)-29H, 31H-phthalocyanine, 2,9,16,23-tetrakis(phenyl thio)-29H, 31H-phthalocyanine, 3,10,17,24-tetra-t-butyl-1,8,15,22-tetrakis-(dimethyl amino)-29H, 31H-phthalocyanine, phthalocyanine tetrasulfonic acid, 4xe2x80x2,4xe2x80x3,4xe2x80x2xe2x80x3,4xe2x80x3xe2x80x3-tetraza-29H, 31H-phthalocyanine, tetracarboxy phthalocyanine, octacarboxy phthalocyanine, naphthalocyanine, 2,11,20,29-tetra-t-butyl-2,3-naphthalocyanine, 5,14,23,32-tetraphenyl-2,3-naphthalocyanine, 5,9,14,18,23,27,32,36-octacarboxy-2,3-naphthalocyanine, etc., or anions, etc., obtained by removing protons therefrom. Preferably, phthalocyanine or naphthalocyanine can be used.
The transition metal complex of the present invention can be obtained by using general methods as described in e.g. xe2x80x9cJikeen kagaku koza 17xe2x80x94Inorganic Complex-Chelate Complex, Fourth Editionxe2x80x9d (in Japanese), Maruzen Co., Ltd., (1991), page 302 etc. Said transition metal complex may be a previously synthesized complex, or the complex may be formed in the reaction system.
The structure of the transition metal complex of the present invention, excluding the ligand and the transition metal atom, is not particularly limited insofar as the catalytic performance is not inactivated. For example, a N,Nxe2x80x2-di(salicylidene)ethylene diaminato iron (II) (also referred to hereinafter as Fe-salen or Fe (II)-salen) transition metal complex, using N,Nxe2x80x2-disalicylidene ethylene diamine (also referred to hereinafter as salen) as the ligand and iron as the transition metal, is known easily to form xcexc-oxo-bis{(N,Nxe2x80x2-disalicylidene ethylene diaminato iron (III))}, which is oxygen crosslinked compound in oxygen, and there are not any problems that this compound is used.
There are cases, which, in the transition metal complex of the present invention, require a counter ion to maintain electrical neutrality. As the counter anion, a conjugated base of Brensted acid is generally used, and specific examples thereof include fluoride ion, chloride ion, bromide ion, iodide ion, sulfate ion, nitrate ion, carbonate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, methane sulfonate ion, trifluoromethane sulfonate ion, toluene sulfonate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, hydroxide ion, oxide ion, methoxide ion, ethoxide ion, etc. As the counter cation, cations such as alkali metals and alkaline earth metals can be used as necessary. Further, the transition metal complex of the present invention may be coordinated with a solvent, etc., in the material of the complex, in the process for synthesizing, and/or in the process of oxidative polymerization.
A co-catalyst may be used to enhance the activity of the transition metal complex of the present invention. The co-catalyst includes amines, diketone complexes, metal halides, etc.
When the amine is used as the co-catalyst, its effects such as improvement of the polymerization activity can be expected as shown in Polymer Bulletin, 42, 125 (1999). As far as the amine species used does not have an effect on the activity of the transition metal complex, and is soluble in the phenol-compound-containing vegetable oil or in the reaction solvent, the amine is not particularly limited, and amine of public knowledge can be used. Specifically, tertiary amines such as pyridine, triethyl amine, 2,6-lutidine, N,N,Nxe2x80x2,Nxe2x80x2-tetraethylene diamine can be used, and the amine is used in the range of preferably 0.001 to 50% by weight, more preferably 0.001 to 10% by weight, relative to the phenol-compound-containing vegetable oil as the material.
The diketone complex includes acetyl acetonato complexes of iron, cobalt, vanadium, chromium, manganese, or nickel. Specifically, bis(acetyl acetonato) cobalt (II), trisacetyl acetonato) cobalt (III), bis(acetyl acetonato) manganese (II), tris(acetyl acetonato) manganese (III), tris(acetyl acetonato) iron (III), bis(acetyl acetonato) oxovanadium (IV), etc., can be mentioned, and these compounds preferably are used in the range of 0.1 to 5 mol equivalent, more preferably 0.5 to 2 mol equivalent, relative to the transition metal complex, which is used.
Specific examples of the metal halides include cobaltous chloride, cobaltic chloride, etc., and these compounds preferably are used in the range of 0.1 to 5 mol equivalent, more preferably 0.5 to 2 mol equivalent, relative to the transition metal complex, which is used.
The oxidizing agent used in the present invention may be arbitrary, and preferably oxygen or peroxides can be used. Oxygen may be a mixture with an inert gas, and may be the air. Examples of the peroxides include hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, peracetic acid, perbenzoic acid, etc. More preferably, a peroxide can be used, and hydrogen peroxide is particularly preferable.
When oxygen is used as the oxidizing agent in the present invention, it is used generally in equivalent to large excess relative to the phenol-compound-containing vegetable oil. When the peroxide is used, it is used generally in an amount of equivalent or more and 3 equivalents or less, preferably 0.8 to 2 equivalents, relative to the phenol-compound-containing vegetable oil.
The phrase xe2x80x9ca solvent is substantially not used to carried out the polymerization reactionxe2x80x9d in the present invention means that the solvent is used such that the concentration of the solvent in the phenol-compound-containing vegetable oil is preferably 0 to 10% by weight, more preferably 1 to 3% by weight, particularly preferably 0% by weight, and in this case, the reaction is carried out desirably at the temperature range at which the reaction medium remains fluid, and in case of using the cashew nut shell liquid, the reaction is carried out desirably at room temperature or more because its melting point is generally room temperature or less. However, when hydrogen peroxide is used as the oxidizing agent, hydrogen peroxide is used generally as 30%, 60%, or the like of aqueous hydrogen peroxide solution, the water content in hydrogen peroxide as the oxidizing agent is not regarded as the solvent in the present invention.
Further, the present invention can also be carried out even in the presence of a solvent. In case of using as a solvent, the solvent is not particularly limited insofar as it is inert to the phenol-compound-containing vegetable oil, is fluid at the reaction temperature, and is capable of dissolving the curable resin composition, which is produced. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, etc.; linear and cyclic aliphatic hydrocarbons such as heptane, cyclohexane, etc.; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, etc.; nitriles such as acetonitrile, benzonitrile, etc.; alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, etc.; ethers such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, etc.; amides such as N,N-dimethyl formamide, N-methyl pyrrolidone, etc.; nitro compounds such as nitromethane, nitrobenzene, etc.; and water, etc. These may be used as singly or as a mixture thereof.
When said solvent is used, the solvent is used such that the concentration of the phenol-compound-containing vegetable oil is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight. The reaction temperature for carrying out the present invention is in the temperature range where the aliphatic unsaturated double bonds in the side chains of the phenol-compound-containing vegetable oil are not modified by heating, and where the reaction medium remains fluid. When the solvent is not used, such temperatures should be in a temperature range of higher than the melting point of the phenol-compound-containing vegetable oil, or higher than the melting point of comonomers if the comonomers are coexistent. The temperature range is preferably 0xc2x0 C. to 180xc2x0 C., more preferably 0xc2x0 C. to 150xc2x0 C. Particularly, the process of the present invention is characterized in that the polymerization reaction can be carried out even under low-temperature conditions in the range of 0 to 40xc2x0 C. Further, for example, when the polymerization reaction is carried out using substantially no solvent in the present invention, particularly by using hydrogen peroxide as the oxidizing agent and Fe (II)-salen contained in the aforementioned formula (II) as the transition metal complex, exothermal reaction may occur upon addition of hydrogen peroxide, and the temperature in the system rise (in the range from the temperature before addition of hydrogen peroxide to about 140xc2x0 C.), which however is not problematic. Further, when the polymerization reaction is carried out using the aforementioned formula (I) or (IV), the reaction temperature is preferably 40 to 180xc2x0 C., more preferably 60 to 180xc2x0 C.
The curable resin composition of the present invention can be further cured by crosslinking in the presence of the oxidizing catalyst. This curing reaction is effective as curing reaction in case of using as coatings, etc., and the so-called metal drier is used as the oxidizing catalyst. The metal drier is not particularly limited insofar as it is a compound with an ability to oxidize unsaturated fatty acids to cause crosslinking reaction, and various metals or salts thereof can be used. Specifically, it can use naphthenate, octylate, or oleate of cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, or copper, preferably can use cobalt naphthenate, lead naphthenate, or manganese naphthenate. Various metal complexes, used as the polymerization catalyst in the present invention, also have an ability as the metal drier, and may just be used without removing them from these reaction system. Further, the metal drier may be used as not only singly but also a mixture of two kinds or more. The amount of addition of the metal drier vary according to the type of the metal drier, etc., the metal drier is generally used preferably in the range of 0.001% by weight to 1% by weight in terms of metal content relative to the curable resin composition.
The molecular weight of the polymer obtained in the present invention is preferably in the range of 350 to 100,000 of number average molecular weight, particular preferably in the range of 500 to 30,000 of number average molecular weight.
In the present invention, the oxidative polymerization reaction of the phenol-compound-containing vegetable oil can be carried out in various modes. For example, a solution of the phenol-compound-containing vegetable oil and a solution of the transition metal complex may be prepared separately and then be introduced into the same vessel, or the metal complex or a solution thereof may be added into a solution of the phenol-compound-containing vegetable oil. In case of addition of hydrogen peroxide, a method of adding the peroxide gradually to a solution of the phenol-compound-containing vegetable oil and the transition metal complex is preferable. Further, besides the method of the aforementioned solution polymerization, there is no problem even if one uses the methods of suspension polymerization and dispersion polymerization, which carried out the reaction of the phenol-compound-containing vegetable oil and the transition metal complex by addition of a dispersion stabilizer to the reaction system, or the method of emulsion polymerization, which carried out the reaction of the phenol-compound-containing vegetable oil and the transition metal complex by addition of an emulsion stabilizer to the reaction system. Additionally, combinations of various methods are usable not as long as the transition metal complex is inactivated. In production of the resin composition of the present invention (including the curable resin composition), there is no problem even if the transition metal complex used in oxidative polymerization may remain as it is in the resin composition without removing from the composition after the reaction.
There is no problem even if vegetable oil monomers containing a remaining phenol compound which do not react yet, or the other monomer components given to copolymerization, additionally the polymer resin that contains the phenol-compound-containing vegetable oil in the transition metal complex, are contained in the resin composition and the curable resin composition of the present invention. Because these monomers are generally viscous at room temperature, they may be used as they are, without using a diluting solvent in the case where these monomers are used at room temperature. In this case, there is no problem insofar as the ratio of the vegetable oil monomers containing remaining phenol compounds in the curable resin composition, or of the other monomer components given to copolymerization, is a range without exerting an influence on the physical properties of the coating film, such as the curing time of the coating film, etc., hardness of the coating film, and the physical properties of the coating film, etc., such as leveling properties of the coating film, wetting properties of the coating film, etc.
Further, as can also be estimated from the fact that cardanol of a constituent component in the aforementioned resin has a similar structure to urushiol of a major component of urushi, the aforementioned resin have characterized that the resulting coating film is similar to a urushi coating film. In this case, polysaccharides and proteins as components other than urushiol in urushi may be added in order to let the resulting coating film resembles a natural urushi coating film more, for example, starch (derivatives), arabic gum, casein, pullulan, gelatin (hydrolysates), etc., can be mentioned.
The curable resin compositions of the present invention can be cured by using various methods. That is, because these resin compositions have an unsaturated double bond in the polymer side chain, or a phenolic hydroxyl group on the site of the aromatic ring, the curable product can be prepared by using a known method based on these reactivity sites to progress a crosslinking reaction. For example, these compositions can be cured by utilizing the aforementioned crosslinking reaction with oxygen or organic peroxides, crosslinking with phenol resin and amino resin, crosslinking with halogen compounds, crosslinking with isocyanates, crosslinking with epoxy compounds, crosslinking by heating, crosslinking by light, crosslinking by UV irradiation, crosslinking by electron beam and y-ray, or the like.
The pencil hardness of the curable resin composition of the present invention, as determined by 8.4.2 Hand Scratching Method in JIS-K5400, can satisfy the condition of 9H to 2B, preferably 9H to HB, within 2 weeks, preferably within 1 week, after the curable resin composition was coated on a base material and then change to a coating film.
In the curable resin composition of the present invention, an phenolic hydroxyl group, which do not react yet, may be contained in the site of the aromatic ring. Further, the side chain has an aliphatic unsaturated double bond. Accordingly, various derivatives can be produced by using these reactive sites. For example, epoxy etherification by reaction of the phenolic hydroxyl group with epichlorohydrin, allyl etherification by allyl chloride, and (meth)acryl derivatizations by esterifying with (meth)acrylic acid (derivatives), and the like, can be mentioned.
The curable resin composition of the present invention may be used after modification with natural rubber or synthetic rubber, with oils such as tung oil, linseed oil, or soybean oil, or with rosin, glycerin, ethylene glycol, pentaerythritol, etc.
Further, the curable resin composition of the present invention, if necessary, can be contained resin components such as phenol resin, rosin-modified phenol resin, alkyd resin, polyester resin, polyamide resin, etc., fat and oil components such as tung oil, linseed oil, dehydrated castor oil, aliphatic acids, etc., a pigment or dye such as yellow, red, deep blue and black pigment, etc., as color agent, filler such as natural rubber, synthetic rubber, wood flour, cellulose, asbestos, glass fiber, woven fablic, nonwoven fabric, etc., releasing agent, solvents of terpine-type, aliphatic-type, or aromatic-type, and auxiliary agent such as leveling improver, thickener, plasticizer, anti-ultraviolet agent, antioxidant, antistatic agent, etc., and can be used in a variety of utilities such as a raw material for a urushi-like coating, a material for forming a coating film, a compound for recording material, a raw material for ink, a raw material for coating, a raw material for adhesive, a raw material for epoxy resin, a raw material for photoresist, a raw material for antioxidant, a molding material, a raw material for laminated material, a raw material for adhesive, a raw material for binder, a raw material of a phenol resin for casting, a raw material of phenol resin for rubber blending, and a raw material of a phenol resin for fiber plate.
According to the present invention, a curable resin composition containing a resin formed in the presence of a transition metal complex by polymerizing the oxidative-polymerizable compound including the phenol-compound-containing vegetable oil component can be obtained under mild conditions. According to the method of the present invention by oxidative polymerization of a phenol-compound-containing vegetable oil by using a specific catalyst, there can be obtained a curable resin composition, that contains a polymer which phenylene bond unit and oxyphenylene bond unit bound at random, and whose an aliphatic unsaturated double bond in the side chain is allowed to remain.
According to the present invention, a curable resin composition preferable as a urushi-like coating, etc., can be obtained without using formalin.
Further, because the method of the present invention does not use formalin as a material, there is no problem of generation of formalin from a product of the resin during and after the stage of production of the resin, and this method is very excellent in the points that they can answer the requirements, of an increasing of consciousness toward environmental problems, a deodorization of living environment, a safety or health for the human body, etc.
The present invention is summarized as follows:
(1) A curable resin composition, comprising a resin formed, in the presence of a transition metal complex, by polymerizing an oxidative-polymerizable compound that contains a phenol-compound-containing vegetable oil.
(2) The curable resin composition according to item (1), which comprises the resin formed, in the presence of a transition metal complex, and oxygen or a peroxide, by polymerizing the oxidative-polymerizable compound that contains a phenol-compound-containing vegetable oil.
(3) The curable resin composition according to item (1) or (2), wherein the phenol-compound-containing vegetable oil is a cashew nut shell liquid.
(4) The curable resin composition according to any one of items (1) to (3), wherein the transition metal complex is a complex represented by the aforementioned formula (I), (II), (III), or (IV).
(5) The curable resin composition according to any one of items (1) to (4), wherein a transition metal in the transition metal complex is iron, cobalt, vanadium, chromium, manganese, nickel, copper, or vanadium oxide.
(6) The curable resin composition according to any one of items (1) to (5), wherein the curable resin composition further comprises a metal drier.
(7) A method for producing a curable resin composition comprising a resin formed, in the presence of a catalyst, by polymerizing an oxidative-polymerizable compound that contains a phenol-compound-containing vegetable oil, wherein the catalyst is a transition metal complex.
(8) The method for producing a curable resin composition according to item (7), which comprises polymerizing the oxidative-polymerizable compound that contains a phenol-compound-containing vegetable oil, in the presence of a transition metal complex, and oxygen or a peroxide.
(9) The method for producing a curable resin composition according to item (7) or (8), wherein the phenol-compound-containing vegetable oil is a cashew nut shell liquid.
(10) The method for producing a curable resin composition according to any one of items (7) to (9), wherein the transition metal complex is a complex represented by the aforementioned formula (I), (II), (III), or (IV).
(11) The method for producing a curable resin composition according to any one of items (7) to (10), the curable resin composition containing a resin formed, in the presence of a catalyst, by polymerizing an oxidative-polymerizable compound that contains a phenol-compound-containing vegetable oil, wherein the polymerization reaction is carried out using substantially no solvent.
(12) A coating resin composition, which contains a metal drier in the curable resin composition described in item (1).